Perovskite composite structure

ABSTRACT

A perovskite composite structure is provided. The perovskite composite structure includes a light absorption layer and a sterically-hindered layer disposed in the periphery of the light absorption layer. The light absorption layer includes a perovskite material. The sterically-hindered layer includes a two-dimensional material.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the priority benefit of China application serialno. 201710092678.0, filed on Feb. 21, 2017. The entirety of theabove-mentioned patent application is hereby incorporated by referenceherein and made a part of this specification.

BACKGROUND OF THE INVENTION Field of the Invention

The invention relates to a composite structure, and more particularly,to a perovskite composite structure.

Description of Related Art

The organic-inorganic hybrid perovskite material has high lightabsorption and high electron mobility, and can change the lightabsorption band via changes in the components thereof, and therefore asolar cell made from the organic-inorganic hybrid perovskite materialhas high efficiency. However, the organic-inorganic hybrid perovskitematerial is limited by technical issues such as (1) moisture andoxygen-proof process environment, (2) unstable product in atmosphericenvironment, and (3) inability to successfully grow a continuouscrystal.

Therefore, the development of a perovskite material suitable for use ina wet process that is stable in atmospheric environment and has highelectron mobility is an important issue for those skilled in the art.

SUMMARY OF THE INVENTION

The invention provides a perovskite composite structure that is stablein atmospheric environment and has high electron mobility.

The perovskite composite structure of the invention includes a lightabsorption layer and a sterically-hindered layer located in theperiphery of the light absorption layer. The light absorption layerincludes a perovskite material. The sterically-hindered layer includes atwo-dimensional material.

In an embodiment of the invention, the perovskite material can have thestructure of formula (1) below:ABX₃  (1),wherein A is ammonia (NH₃), methylamine (CH₃NH₂), methanimidamide(CH₄N₂), aminomethanamidine (HNC(NH₂)₂), formamidine (HC(NH)NH₂),ethylenediamine (C₂H₄(NH₂)₂), dimethylamine ((CH₃)₂NH), imidazole(C₃H₄N₂), acetamidine (CH₃CNHNH₂), propylamine (C₃H₇NH₂), isopropylamine(iso-C₃H₇NH₂), trimethylenediamine (CH₂)₃(NH₂)₂), ethylamine, butylamine(C₄H₉NH₂), isobutylamine (iso-C₄H₉NH₂), tert-butylamine ((CH₃)₃CNH₂),diethylamine ((C₂H₅)₂NH), 5-aminovaleric acid (NH₂(CH₂)₄COOH),thiophenemethylamine (C₅H₇NS), hexylamine (C₆H₁₃NH₂), aniline (C₆H₅NH₂),benzylamine (C₆H₅CH₂NH₂), phenylethylamine (C₆H₅C₂H₄NH₂), octylamine(C₈H₁₇NH₂), decylamine (C₁₀H₂₁NH₂), dodecylamine (C₁₂H₂₅NH₂),tetradecylamine (C₁₄H₂₉NH₂), hexadecylamine (C₁₆H₃₃NH₂), oleylamine(C₁₈H₃₅NH₂), octadecylamine (C₁₈H₃₇NH₂), eicosylamine (C₂₀H₄₁NH₂), Li,Na, K, Rb, Cs, or Cu; B is Cd, Co, Cr, Cu, Fe, Ge, Pb, or Sn; and X isCl, Br, I, cyanide (CN), cyanate (NCO), thiocyanate (NCS), selenocyanate(SeCN), or tellurocyanate (TeCN).

In an embodiment of the invention, the two-dimensional material is, forinstance, bismuth sulfide (Bi₂S₃) black phosphorus, hexagonal boronnitride (h-BN), graphene, graphene oxide (GO), reduced graphene oxide(rGO), indium selenide (In₂Se₃), lead tin disulfide (PbSnS₂),phosphorene, arsenic sulfide (As₂S₃), antimony arsenic sulfide (SbAsS₃);monochalcogenide (MX) such as bismuth thallium telluride (BiTlTe),copper sulfide (CuS), gallium selenide (GaSe), gallium selenidetelluride (GaSeTe), gallium sulfide (GaS), gallium sulfide selenide(GaSSe), gallium telluride (GaTe), germanium selenide (GeSe), germaniumsulphide (GeS), indium selenide (InSe), indium telluride (InTe),thallium selenide (TlSe), tin selenide (SnSe), thallium galliumdisulfide (TlGaS₂), thallium gallium diselenide (TlGaSe₂), thalliumindium disulfide (TlInS₂); dichalcogenide (MX₂) such as hafniumdiselenide (HfSe₂), hafnium disulfide (HfS₂), molybdenum diselenide(MoSe₂), molybdenum disulfide (MoS₂), molybdenum sulfide selenide(MoSSe), molybdenum tungsten diselenide (MoWSe₂), molybdenum tungstendisulfide (MoWS₂), tungsten disulfide (WS₂), tungsten diselenide (WSe₂),rhenium diselenide (ReSe₂), tantalum disulfide (TaS₂), tin diselenide(SnSe₂), tin disulfide (SnS₂), rhenium molybdenum disulfide (ReMoS₂),rhenium niobium diselenide (ReNbSe₂), rhenium niobium disulfide(ReNbS₂), tungsten ditelluride (WTe₂), tungsten sulfide selenide (WSSe),zirconium diselenide (ZrSe₂), zirconium disulfide (ZrS₂), zirconiumditelluride (ZrTe₂); trichalcogenide (MX₃) such as titanium trisulfide(TiS₃); iodide (MI₂) such as cadmium diiodide (CdI₂), lead diiodide(PbI₂), or a combination thereof (including one or more).

In an embodiment of the invention, the light absorption layer canfurther include the two-dimensional material.

In an embodiment of the invention, the sterically-hindered layer furtherincludes organic amine.

In an embodiment of the invention, the organic amine is, for instance,ammonia, methylamine, methanimidamide, aminomethanamidine, formamidine,ethylenediamine, dimethylamine, imidazole, acetamidine, propylamine,isopropylamine, trimethylenediamine, ethylamine, butylamine,isobutylamine, tert-butylamine, diethylamine, 5-aminovaleric acid,thiophenemethylamine, hexylamine, aniline, benzylamine,phenylethylamine, octylamine, decylamine, dodecylamine, tetradecylamine,hexadecylamine, oleylamine, octadecylamine, eicosylamine, or acombination thereof (including one or more).

In an embodiment of the invention, the length of the two-dimensionalmaterial is, for instance, 0.5 μm to 10 μm.

Based on the above, in the perovskite composite structure of theinvention, the sterically-hindered layer located in the periphery of thelight absorption layer having a perovskite material can block moistureand air, and is therefore stable in atmospheric environment. Moreover,since the light absorption layer and/or the sterically-hindered layer ofthe perovskite composite structure of the invention includes atwo-dimensional material, the electron transport capability of theperovskite can be increased.

In order to make the aforementioned features and advantages of thedisclosure more comprehensible, embodiments accompanied with FIGURES aredescribed in detail below.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings are included to provide a furtherunderstanding of the invention, and are incorporated in and constitute apart of this specification. The drawings illustrate embodiments of theinvention and, together with the description, serve to explain theprinciples of the invention.

FIG. 1 is a cross-sectional schematic diagram of a perovskite compositestructure according to an embodiment of the invention.

DESCRIPTION OF THE EMBODIMENTS

FIG. 1 is a cross-sectional schematic diagram of a perovskite compositestructure according to an embodiment of the invention.

Referring to FIG. 1, a perovskite composite structure 100 of the presentembodiment includes a light absorption layer 110 and asterically-hindered layer 120. The light absorption layer 110 includes aperovskite material. In the invention, “perovskite material” refers to amaterial having a “perovskite structure” and not calcium titanate(CaTiO₃) in particular. In other words, “perovskite material” containsany material having a crystal structure of a similar type to perovskiteoxide. The perovskite material has the structure shown in formula (1)below:ABX₃  (1),wherein A and B are cations and X is an anion. The A cation ismonovalent and the B cation is divalent.

For instance, in the present embodiment, A is, for instance, ammonia,methylamine, methanimidamide, aminomethanamidine, formamidine,ethylenediamine, dimethylamine, imidazole, acetamidine, propylamine,isopropylamine, trimethylenediamine, ethylamine, butylamine,isobutylamine, tert-butylamine, diethylamine, 5-aminovaleric acid,thiophenemethylamine, hexylamine, aniline, benzylamine,phenylethylamine, octylamine, decylamine, dodecylamine, tetradecylamine,hexadecylamine, oleylamine, octadecylamine, eicosylamine, Li, Na, K, Rb,Cs, or Cu; and B is Cd, Co, Cr, Cu, Fe, Ge, Pb, or Sn; and X is Cl, Br,I, cyanide (CN), cyanate (NCO), thiocyanate (NCS), selenocyanate (SeCN),or tellurocyanate (TeCN), but the invention is not limited thereto. Inother words, the perovskite material of the present embodiment is anorganic-inorganic hybrid perovskite material formed by an inorganicmaterial and an organic material.

Since the organic-inorganic hybrid perovskite material of the inventionis a material formed by mixing, the organic-inorganic hybrid perovskitematerial of the invention has the characteristics of both an organiccompound and an inorganic crystal. The inorganic component is formed bya framework covalently bonded and ionic interaction, and can providehigh carrier mobility. The organic component facilitates theself-assembly mechanism of the materials. Moreover, the electricalproperties of the organic and inorganic materials can be adjusted bylowering the dimensionality of the organic component and the electroniccoupling between inorganic sheet materials.

In the present embodiment, the light absorption layer 110 can furtherinclude a two-dimensional material. The two-dimensional material is, forinstance, bismuth sulfide (Bi₂S₃) black phosphorus, hexagonal boronnitride (h-BN), graphene, graphene oxide (GO), reduced graphene oxide(rGO), indium selenide (In₂Se₃), lead tin disulfide (PbSnS₂),phosphorene, arsenic sulfide (As₂S₃), antimony arsenic sulfide (SbAsS₃);monochalcogenide (MX) such as bismuth thallium telluride (BiTlTe),copper sulfide (CuS), gallium selenide (GaSe), gallium selenidetelluride (GaSeTe), gallium sulfide (GaS), gallium sulfide selenide(GaSSe), gallium telluride (GaTe), germanium selenide (GeSe), germaniumsulphide (GeS), indium selenide (InSe), indium telluride (InTe),thallium selenide (TlSe), tin selenide (SnSe), thallium galliumdisulfide (TlGaS₂), thallium gallium diselenide (TlGaSe₂), thalliumindium disulfide (TlInS₂); dichalcogenide (MX₂) such as hafniumdiselenide (HfSe₂), hafnium disulfide (HfS₂), molybdenum diselenide(MoSe₂), molybdenum disulfide (MoS₂), molybdenum sulfide selenide(MoSSe), molybdenum tungsten diselenide (MoWSe₂), molybdenum tungstendisulfide (MoWS₂), tungsten disulfide (WS₂), tungsten diselenide (WSe₂),rhenium diselenide (ReSe₂), tantalum disulfide (TaS₂), tin diselenide(SnSe₂), tin disulfide (SnS₂), rhenium molybdenum disulfide (ReMoS₂),rhenium niobium diselenide (ReNbSe₂), rhenium niobium disulfide(ReNbS₂), tungsten ditelluride (WTe₂), tungsten sulfide selenide (WSSe),zirconium diselenide (ZrSe₂), zirconium disulfide (ZrS₂), zirconiumditelluride (ZrTe₂); trichalcogenide (MX₃) such as titanium trisulfide(TiS₃); iodide (MI₂) such as cadmium diiodide (CdI₂), lead diiodide(PbI₂), or a combination thereof (including one or more), but theinvention is not limited thereto. The length of the two-dimensionalmaterial is, for instance, 0.2 μm to 20 μm. In the present embodiment,since the light absorption layer 110 includes a two-dimensional materialhaving high electron mobility, the electron transport capability andlight conversion efficiency of perovskite can be increased.

The sterically-hindered layer 120 is located in the periphery of thelight absorption layer 110. The sterically-hindered layer 120 caninclude a two-dimensional material. The two-dimensional material is, forinstance, bismuth sulfide (Bi₂S₃) black phosphorus, hexagonal boronnitride (h-BN), graphene, graphene oxide (GO), reduced graphene oxide(rGO), indium selenide (In₂Se₃), lead tin disulfide (PbSnS₂),phosphorene, arsenic sulfide (As₂S₃), antimony arsenic sulfide (SbAsS₃);monochalcogenide (MX) such as bismuth thallium telluride (BiTlTe),copper sulfide (CuS), gallium selenide (GaSe), gallium selenidetelluride (GaSeTe), gallium sulfide (GaS), gallium sulfide selenide(GaSSe), gallium telluride (GaTe), germanium selenide (GeSe), germaniumsulphide (GeS), indium selenide (InSe), indium telluride (InTe),thallium selenide (TlSe), tin selenide (SnSe), thallium galliumdisulfide (TlGaS₂), thallium gallium diselenide (TlGaSe₂), thalliumindium disulfide (TlInS₂); dichalcogenide (MX₂) such as hafniumdiselenide (HfSe₂), hafnium disulfide (HfS₂), molybdenum diselenide(MoSe₂), molybdenum disulfide (MoS₂), molybdenum sulfide selenide(MoSSe), molybdenum tungsten diselenide (MoWSe₂), molybdenum tungstendisulfide (MoWS₂), tungsten disulfide (WS₂), tungsten diselenide (WSe₂),rhenium diselenide (ReSe₂), tantalum disulfide (TaS₂), tin diselenide(SnSe₂), tin disulfide (SnS₂), rhenium molybdenum disulfide (ReMoS₂),rhenium niobium diselenide (ReNbSe₂), rhenium niobium disulfide(ReNbS₂), tungsten ditelluride (WTe₂), tungsten sulfide selenide (WSSe),zirconium diselenide (ZrSe₂), zirconium disulfide (ZrS₂), zirconiumditelluride (ZrTe₂); trichalcogenide (MX₃) such as titanium trisulfide(TiS₃); iodide (MI₂) such as cadmium diiodide (CdI₂), lead diiodide(PbI₂), or a combination thereof (including one or more), but theinvention is not limited thereto. The length of the two-dimensionalmaterial is, for instance, 0.2 μm to 20 μm. In the present embodiment,since the sterically-hindered layer 120 includes the two-dimensionalmaterial and is located in the periphery of the light absorption layer110, stereoscopic blocking function is achieved to block moisture. Inother words, the sterically-hindered layer 120 can prevent contact ofmoisture and air with the light absorption layer 110 (in particular theperovskite material in the light absorption layer 110), and thereforethe perovskite composite structure of the invention is relatively stablein atmospheric environment.

Moreover, in the present embodiment, since the two-dimensional materialin the sterically-hindered layer 120 has high electron mobility, thesterically-hindered layer 120 can increase the electron transportcapability and light conversion efficiency of perovskite.

In the present embodiment, the sterically-hindered layer 120 can furtherinclude organic amine. The organic amine is, for instance, ammonia,methylamine, methanimidamide, aminomethanamidine, formamidine,ethylenediamine, dimethylamine, imidazole, acetamidine, propylamine,isopropylamine, trimethylenediamine, ethylamine, butylamine,isobutylamine, tert-butylamine, diethylamine, 5-aminovaleric acid,thiophenemethylamine, hexylamine, aniline, benzylamine,phenylethylamine, octylamine, decylamine, dodecylamine, tetradecylamine,hexadecylamine, oleylamine, octadecylamine, eicosylamine, or acombination thereof (including one or more). In the present embodiment,the organic amine in the sterically-hindered layer 120 has a functionsimilar to “passivation” and can prevent contact of moisture and airwith the light absorption layer 110 (in particular the perovskitematerial in the light absorption layer 110), and therefore theperovskite composite structure of the invention is relatively stable inatmospheric environment.

Based on the above, in the perovskite composite structure of theinvention, the sterically-hindered layer located in the periphery of thelight absorption layer having a perovskite material can block moistureand air, and is therefore stable in atmospheric environment. Moreover,since the light absorption layer and/or the sterically-hindered layer ofthe perovskite composite structure of the invention includes atwo-dimensional material, the electron transport capability of theperovskite can be increased. Since the perovskite composite structure ofthe invention has advantages such as stability in atmosphericenvironment, high electron transport capability, and high lightconversion efficiency, the perovskite composite structure of theinvention is suitable for, for instance, a highly-sensitive light sensorand solar cell.

Although the invention has been described with reference to the aboveembodiments, it will be apparent to one of ordinary skill in the artthat modifications to the described embodiments may be made withoutdeparting from the spirit of the invention. Accordingly, the scope ofthe invention is defined by the attached claims not by the abovedetailed descriptions.

What is claimed is:
 1. A perovskite composite structure, comprising: alight absorption layer comprising a perovskite material, wherein theperovskite material has a structure of formula (1) below:ABX₃  (1), wherein A is ammonia, methylamine, methanimidamide,aminomethanamidine, formamidine, ethylenediamine, dimethylamine,imidazole, acetamidine, propylamine, isopropylamine,trimethylenediamine, ethylamine, butylamine, isobutylamine,tert-butylamine, diethylamine, 5-aminovaleric acid,2-thienylmethylamine, hexylamine, aniline, benzylamine, phenyl ethylamine, octylamine, decylamine, dodecylamine, tetradecylamine,hexadecylamine, oleylamine, octadecylamine, eicosylamine, Li, Na, K, Rb,Cs, or Cu; B is Cd, Co, Cr, Cu, Fe, Ge, Pb, or Sn; and X is Cl, Br, I,cyanide (CN), cyanate (NCO), thiocyanate (NCS), selenocyanate (SeCN), ortellurocyanate (TeCN); and a sterically-hindered layer located in aperiphery of the light absorption layer, wherein the sterically-hinderedlayer comprises a two-dimensional material which is different from theperovskite material, and the two-dimensional material comprises bismuthsulfide (Bi₂S₃) black phosphorus, hexagonal boron nitride (h-BN),graphene, graphene oxide (GO), reduced graphene oxide (rGO), indiumselenide (In₂Se₃), lead tin disulfide (PbSnS₂), phosphorene, arsenicsulfide (As₂S₃), antimony arsenic sulfide (SbAsS₃); monochalcogenide(MX), wherein MX is bismuth thallium telluride (BiTlTe), copper sulfide(CuS), gallium selenide (GaSe), gallium selenide telluride (GaSeTe),gallium sulfide (GaS), gallium sulfide selenide (GaSSe), galliumtelluride (GaTe), germanium selenide (GeSe), germanium sulphide (GeS),indium selenide (InSe), indium telluride (InTe), thallium selenide(TlSe), tin selenide (SnSe), thallium gallium disulfide (TlGaS₂),thallium gallium diselenide (TlGaSe₂), thallium indium disulfide(TlInS₂); dichalcogenide (MX₂), wherein MX₂ is hafnium diselenide(HfSe₂), hafnium disulfide (HfS₂), molybdenum diselenide (MoSe₂),molybdenum disulfide (MoS₂), molybdenum sulfide selenide (MoSSe),molybdenum tungsten diselenide (MoWSe₂), molybdenum tungsten disulfide(MoWS₂), tungsten disulfide (WS₂), tungsten diselenide (WSe₂), rheniumdiselenide (ReSe₂), tantalum disulfide (TaS₂), tin diselenide (SnSe₂),tin disulfide (SnS₂), rhenium molybdenum disulfide (ReMoS₂), rheniumniobium diselenide (ReNbSe₂), rhenium niobium disulfide (ReNbS₂),tungsten ditelluride (WTe₂), tungsten sulfide selenide (WSSe), zirconiumdiselenide (ZrSe₂), zirconium disulfide (ZrS₂), zirconium ditelluride(ZrTe₂); trichalcogenide (MX₃), wherein MX₃ is titanium trisulfide(TiS₃); iodide (MI₂), wherein MI₂ is cadmium diiodide (CdI₂) leaddiiodide (PbI₂) or a combination thereof.
 2. The perovskite compositestructure of claim 1, wherein the light absorption layer furthercomprises the two-dimensional material.
 3. The perovskite compositestructure of claim 2, wherein the sterically-hindered layer furthercomprises an organic amine.
 4. The perovskite composite structure ofclaim 3, wherein the organic amine comprises ammonia, methyl amine,methanimidamide, aminomethanamidine, formamidine, ethylenediamine,dimethylamine, imidazole, acetamidine, propylamine, isopropylamine,trimethylenediamine, ethylamine, butylamine, isobutylamine,tert-butylamine, diethylamine, 5-aminovaleric acid,thiophenemethylamine, hexylamine, aniline, benzylamine,phenylethylamine, octylamine, decylamine, dodecylamine, tetradecylamine,hexadecylamine, oleylamine, octadecylamine, eicosylamine, or acombination thereof.
 5. The perovskite composite structure of claim 1,wherein a length of the two-dimensional material in thesterically-hindered layer is 0.2 μm to 20 μm.
 6. The perovskitecomposite structure of claim 2, wherein a length of the two-dimensionalmaterial in the light absorption layer is 0.2 μm to 20 μm.